Thioheterocyclic near-infrared absorbing dyes

Abstract

Disclosed is a novel near-infrared absorbing dye of formula: ##STR1## wherein X 1 , X 2 independently represents --CR 8 R 9 --, --S--, --Se--, --NR 10 --, --CH═CH-- or --O--; n is an integer of 2 or 3; R 1 and R 2 independently represent alkyl of 1 to 10 carbons or substituted alkyl of 1 to 10 carbons; R 3 represents a ring chosen from a set consisting of aryl, substituted aryl, and a heterocyclic ring of a type present in photographic emulsions; R 4 , R 5 , R 6 and R 7 independently represent hydrogen, alkyl of 1-10 carbons, substituted alkyl of 1-10 carbons, R 4 and R 5 taken together or R 6 and R 7 taken together can represent atoms necessary to form a 5 or 6-membered aliphatic ring, an aromatic six-membered ring, an aromatic 10-membered ring, a substituted aromatic six-member ring or a substituted aromatic 10-member ring; R 8 , R 9 independently represent alkyl of 1-10 carbons, substituted alkyl of 1-10 carbons, aryl of 6-10 carbons, or substituted aryl of 6-10 carbons; and R 10 represents an alkyl of 1-10 carbons, substituted alkyl of 1-10 carbons, aryl of 6-10 carbons, or substituted aryl of 6-10 carbons; with the proviso that when R 3 is phenyl or substituted phenyl and n=3, R 1 or R 2 is not an unsubstituted alkyl.

What is claimed is: 
     
       1. A dye of formula: ##STR11## wherein X 1  and X 2  independently represents --O--; n is an integer of 2 or 3;   R 1  and R 2  independently represent alkyl of 1 to 10 carbons or an alkyl of 1 to 10 carbons substituted with at least one substituent chosen from a group consisting of sulfonate, carboxyl, hydroxy, halogen, carbonylalkyl, amine, aryl or --OL 1 , where L 1  is an alkyl of 1-10 carbons;   R 3  represents an aryl ring, or an aryl substituted with at least one substituent chosen from a group consisting of sulfonate, carboxyl, hydroxy, halogen, carbonylalkyl, amine, aryl or --OL 2 , where L 2  is an alkyl of 1-10 carbons;   R 4  and R 5  independently represent hydrogen, alkyl of 1-10 carbons or an alkyl of 1-10 carbons substituted with at least one substituent chosen from a group consisting of sulfonate, carboxyl, hydroxy, halogen, carbonylalkyl, amine, aryl or --OL 3 , where L 3  is an alkyl of 1-10 carbons, or R 4  and R 5  taken together represent the atoms necessary to form a 5 or 6-membered aliphatic ring, an aromatic six-membered ring, an aromatic 10-membered ring, an aromatic six-member ring substituted with at least one substituent chosen from a group consisting of sulfonate, carboxyl, hydroxy, halogen, carbonylalkyl, amine, aryl or --OL 4 , where L 4  is an alkyl of 1-10 carbons or an aromatic 10-member ring substituted with at least one substituent chosen from a group consisting of sulfonate, carboxyl, hydroxy, halogen, carbonylalkyl, amine, aryl or --OL 5 , where L 5  is an alkyl of 1-10 carbons;   R 6  and R 7  independently represent hydrogen, alkyl of 1-10 carbons or an alkyl of 1-10 carbons substituted with at least one substituent chosen from a group consisting of sulfonate, carboxyl, hydroxy, halogen, carbonylalkyl, amine, aryl or --OL 6 , where L 6  is an alkyl of 1-10 carbons, or R 6  and R 7  taken together represent atoms necessary to form a 5 or 6-membered aliphatic ring, an aromatic six-membered ring, an aromatic 10-membered ring, an aromatic six-member ring substituted with at least one substituent chosen from a group consisting of sulfonate, carboxyl, hydroxy, halogen, carbonylalkyl, amine, aryl or --OL 7 , where L 7  is an alkyl of 1-10 carbons or an aromatic 10-member ring substituted with at least one substituent chosen from a group consisting of sulfonate, carboxyl, hydroxy, halogen, carbonylalkyl, amine, aryl or --OL 8 , where L 8  is an alkyl of 1-10 carbons; and   Z is an anion or cation suitable to balance the charge.   
     
     
       2. The dye recited in claim 1, wherein at least one of R 1  and R 2  is an alkyl of 1 to 10 carbon atoms substituted with sulfonate or carbonate. 
     
     
       3. The dye recited in claim 1, wherein R4 and R5 or R6 and R7 are taken together to form a six-membered aromatic ring or a 10-membered aromatic ring. 
     
     
       4. The dye recited in claim 3, wherein said six-membered aromatic ring or said 10-membered aromatic ring is substituted with sulfonate or carboxylate. 
     
     
       5. The dye recited in claim 1, wherein R 1  or R 2  is an alkyl of 1-10 carbon atoms substituted with a sulfonate or carboxylate and at least one combination of R 4  and R 5  or R 6  and R 7  are taken together to form a six-membered aromatic ring or a 10membered aromatic ring wherein said six-membered aromatic ring or said 10-membered aromatic ring is substituted with a sulfonate or a carboxylate. 
     
     
       6. The dye recited in claim 5, wherein R 1  or R 2  is an alkyl of 1-5 carbons atoms. 
     
     
       7. The dye recited in claim 8, wherein R 3  is chosen from a group consisting of benzothiazole, pyrimidine, benzoxazole, phenyltetrazole, and methyl triazole. 
     
     
       8. A dye of formula: ##STR12## wherein X 1  and X 2  independently represents --O--; n is an integer of 2 or 3;   R 1  and R 2  independently represent alkyl of 1 to 10 carbons or an alkyl of 1 to 10 carbons substituted with at least one substituent chosen from a group consisting of sulfonate, carboxyl, hydroxy, halogen, carbonylalkyl, amine, aryl or --OL 1 , where L 1  is an alkyl of 1-10 carbons;   R 3  represents a heterocyclic ring containing atoms chosen from a group consisting of C, N, O, S and Se;   R 4  and R 5  independently represent hydrogen, alkyl of 1-10 carbons or an alkyl of 1-10 carbons substituted with at least one substituent chosen from a group consisting of sulfonate, carboxyl, hydroxy, halogen, carbonylalkyl, amine, aryl or --OL 2 , where L 2  is an alkyl of 1-10 carbons, or R 4  and R 5  taken together represent the atoms necessary to form a 5 or 6-membered aliphatic ring, an aromatic six-membered ring, an aromatic 10-membered ring, an aromatic six-member ring substituted with at least one substituent chosen from a group consisting of sulfonate, carboxyl, hydroxy, halogen, carbonylalkyl, amine, aryl or --OL 3 , where L 3  is an alkyl of 1-10 carbons, or an aromatic 10-member ring substituted with at least one substituent chosen from a group consisting of sulfonate, carboxyl, hydroxy, halogen, carbonylalkyl, amine, aryl or --OL 4 , where L 4  is an alkyl of 1-10 carbons;   R 6  and R 7  independently represent hydrogen, alkyl of 1-10 carbons or an alkyl of 1-10 carbons substituted with at least one substituent chosen from a group consisting of sulfonate, carboxyl, hydroxy, halogen, carbonylalkyl, amine, aryl or --OL 5 , where L 5  is an alkyl of 1-10 carbons, or R 6  and R 7  taken together represent atoms necessary to form a 5 or 6-membered aliphatic ring, an aromatic six-membered ring, an aromatic 10-membered ring, an aromatic six-member ring substituted with at least one substituent chosen from a group consisting of sulfonate, carboxyl, hydroxy, halogen, carbonylalkyl, amine, aryl or --OL 6 , where L 6  is an alkyl of 1-10 carbons or an aromatic 10-member ring substituted with at least one substituent chosen from a group consisting of sulfonate, carboxyl, hydroxy, halogen, carbonylalkyl, amine, aryl or --OL 7 , where L 7  is an alkyl of 1-10 carbons; and   Z is an anion or cation suitable to balance the charge.   
     
     
       9. The dye recited in claim 8, wherein at least one of R 1  and R 2  is an alkyl of 1 to 10 carbon atoms substituted with sulfonate or carbonate. 
     
     
       10. The dye recited in claim 8, wherein R 4  and R 5  or R 6  and R 7  are taken together to form a six-membered aromatic ring or a 10-membered aromatic ring. 
     
     
       11. The dye recited in claim 10, wherein said six-membered aromatic ring or said 10-membered aromatic ring is substituted with sulfonate or carboxylate. 
     
     
       12. The dye recited in claim 8, wherein R 1  or R 2  is an alkyl of 1-10 carbon atoms substituted with a sulfonate or carboxylate and at least one combination of R 4  and R 5  or R 6  and R 7  are taken together to form a six-membered aromatic ring or a 10-membered aromatic ring wherein said six-membered aromatic ring or said 10-membered aromatic ring is substituted with a sulfonate or a carboxylate. 
     
     
       13. The dye recited in claim 12, wherein R 1  or R 2  is an alkyl of 1-5 carbons.